JP6969776B2 - Allergen reduction composition - Google Patents

Description

The present invention has an allergen-reducing composition for reducing allergens such as mites and pollen, or for imparting a function of reducing allergens to non-woven fabrics, wallpaper, filter materials, fibers or textile products, building interior materials, and the like. Regarding things.

Allergic diseases such as asthma, atopic dermatitis, and allergic rhinitis are plagued by many people, and have been increasing in recent years. The causes of these allergic diseases are various allergens existing in the environment, and among them, mites, pet hair, pollen, and mold that live indoors are typical inhalable allergens. Well known. In particular, house dust mite, which is a dust mite that inhabits the house, has become a major problem as a source of allergens. For house dust mite, textile products such as tatami mats, rugs, bedding, and curtains, or even outdoors, seat fabrics for moving vehicles such as trains and automobiles are hotbeds for growth.

Among the house dust mites, Dermatophagoides farinae and Dermatophagoides pteronysinus are typical species, and the carcasses and feces of these mites are strong allergen substances. In addition, pollen of various plants, including pollen of Sugi (Cryptomeria japonica ) scattered in early spring, is also an allergen and causes allergic rhinitis in particular. There are many types of pollen scattered throughout the year, including not only cedar pollen in early spring, but also hinoki, mugwort, ragweed, and Dactylis, and there is a risk of causing allergies due to pollen at any time. It is thought that there is.

In order to remove such allergens such as mites and pollen, there is a method of passing air through the filter using an air conditioner or an air purifier, but only allergens that fly in the air can be removed, and allergens on the filter. It results in the collection of substances and there is a risk of re-scattering of allergens when replacing the filter. In addition, masks are used to prevent inhalation of pollen such as sugi, but pollen adhering to the mask does not lose its allergenicity, so there is a risk that it will be absorbed by re-scattering. .. Vacuum cleaners are effective as a method of removing allergens, but a large amount of allergens contained in the sucked dust is only stored in the dust collection bag, and there is a risk that the allergens will be scattered again when the dust collection bag is discarded. Be done.

Tannic acid has long been known as a drug for reducing or removing allergenicity of allergen substances, and a method of applying a polyphenol compound such as tannic acid has been proposed. For example, a method of using tannin acid as an allergen inactivating agent (Patent Document 1), tea extract, hydroxyapatite, epicatechin, epigallocatechin, epicatechin gallate, epigallocatechin gallate, gallic acid and gallic acid. A method of using an ester with an alcohol having 1 to 4 carbon atoms as an allergen inactivating agent (Patent Document 2) is disclosed. Tannic acid is an excellent agent because it is a highly safe natural product and has an excellent allergen-reducing effect, but it is colored brown and coloring progresses over time. This has the problem of limiting its use.

As the allergen reduction composition using a zinc compound, an inorganic salt compound of zinc such as zinc oxide, zinc chloride, zinc sulfate and zinc nitrate, and a water-soluble zinc compound such as zinc acetate are used as an allergen-reducing component and removal. It has been proposed as an agent, a neutralizing composition or an inactivating agent, and a zinc salt of hydroxy acid has also been proposed as an allergen reducing agent (Patent Documents 5 to 9). Further, an allergen-reducing composition using a zirconium salt has also been proposed (Patent Document 10).

Japanese Unexamined Patent Publication No. 61-44821 Japanese Unexamined Patent Publication No. 6-279273 Japanese Unexamined Patent Publication No. 2006-239393 Japanese Unexamined Patent Publication No. 2007-39620 Japanese Unexamined Patent Publication No. 2003-96670 Japanese Unexamined Patent Publication No. 2004-189606 Japanese Patent Publication No. 2004-510841 Japanese Unexamined Patent Publication No. 2006-239393 WO2015 / 141712 Publication Japanese Unexamined Patent Publication No. 2001-214376

Allergen reduction compositions that can reduce allergens such as ticks and cedar pollen, and can impart the function of reducing allergens to non-woven fabrics, wallpaper, filter materials, textiles or textile products, building interior materials, etc., and these. It is an object of the present invention to provide a non-woven fabric, wallpaper, filter material, fiber or textile product, and building interior material processed from the allergen-reducing composition of the above.

As a result of diligent research to solve such problems, the present inventors have found that a composition containing both a compound containing zinc and a compound containing a water-soluble zirconium salt dramatically reduces allergens. We have found that this composition can reduce allergens such as mite and Japanese cedar pollen by exhibiting the effect, and completed the present invention.

That is, the present invention is (1) an allergen-reducing composition containing a zinc-containing compound and a water-soluble zirconium salt, and (2) an allergen-reducing composition in which the water-soluble zirconium salt is a basic zirconium carbonate. Yes, (3) an allergen-reducing composition in which the zinc-containing compound is at least one selected from zinc hydroxyate, zinc carbonate, basic zinc carbonate, zinc oxide or zinc hydroxide, and (4) the above. It is a surface treatment agent containing the allergen-reducing composition of the above and water or a water-soluble solvent. It is a material.

Using the allergen-reducing composition of the present invention, interiors such as indoor floors, carpets, sofas, wallpaper, curtains, bedding such as duvet side areas, duvet covers, duvet batting, sheets, pillowcases, mats, cars, cars. It is possible to provide an agent that can be sprayed on automobile parts such as sheets and car mats, stuffed fabrics, etc., and by processing it into non-woven fabrics, wallpaper, filter materials, textiles or textile products, building interior materials, etc. It is possible to provide filter materials having a function of reducing allergens such as ticks and cedar pollen, non-woven fabrics such as masks, textiles or textile products, floor materials, ceiling materials, wallpaper and other building interior materials.

As the zinc-containing compound used in the present invention, those commercially available as reagents or industrial raw materials can be generally used. Examples thereof include inorganic zinc salts such as zinc sulfate and zinc chloride, organic acid zinc salts such as zinc acetate and zinc propionate, and water-insoluble zinc compounds such as zinc oxide, zinc hydroxide, zinc carbonate and basic zinc carbonate. However, from the viewpoint of safety, zinc salts of hydroxy acid, zinc oxide, zinc hydroxide, zinc carbonate, and basic zinc carbonate are preferable. The hydroxy acid is a carboxylic acid having one or more hydroxyl groups, and specific examples thereof include glycolic acid, glyceric acid, gluconic acid, glucuronic acid, lactic acid, tartronic acid, 2-hydroxybutyric acid, and 3-hydroxybutyric acid. , Apple acid, tartrate acid, citramalic acid, citric acid, isocitrate, leucic acid, mevalonic acid, pantoic acid, lysynolic acid, shikimic acid and the like, of which gluconic acid, citric acid, lactic acid are preferable, and gluconic acid is further used. Is more preferable. Specific preferred zinc hydroxyaates include zinc gluconate, zinc citrate, and zinc lactate, with zinc gluconate being more preferred. Zinc gluconate has an acute oral toxicity of more than 5000 mg / kg in rats, is extremely safe, and is used as a food substitute for breast milk and as a food with health claims for the purpose of prevention and treatment of zinc deficiency. .. Examples of the water-insoluble zinc include zinc oxide, zinc hydroxide, zinc carbonate and the like, and among these, zinc carbonate is preferable.

The above-mentioned zinc hydroxyate can be synthesized by reacting an aqueous solution of a hydroxy acid with an alkali metal hydroxide to neutralize it, and further reacting it with a water-soluble zinc salt. Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like, and sodium hydroxide is preferable. Examples of the water-soluble zinc salt include zinc chloride and zinc bromide, and zinc chloride is preferable.

As the water-soluble zirconium salt used in the present invention, those commercially available as reagents or industrial raw materials can be generally used. For example, zirconium chloride, zirconium bromide, zirconium oxychloride, zirconium sulfate, zirconium nitrate, zirconium carbonate, zirconium ammonium carbonate, zirconium acetate, potassium zirconium carbonate, basic zirconium carbonate salt (basic zirconium carbonate ammonium, basic zirconium carbonate potassium, etc.) ), Basic zirconium chloride and the like, of which the basic zirconium carbonate salt is preferred. The ratio of the zinc-containing compound to the water-soluble zirconium salt is preferably 1: 9 to 9: 1 as a weight ratio, and more preferably 2: 8 to 8: 2.

The allergens targeted by the allergen-reducing composition of the present invention include allergens derived from Dermatophagoides pteronyssinus (Dermatophagoides pteronyssinus), allergens derived from worms (Der p2), and Dermatophagoides vulgaris (Dermatophagoides ). Examples include allergens (Der f1) and allergens derived from worms (Der f2). Examples of plant-derived allergens include allergens derived from pollen of Sugi (Cryptomeria japonica ), hinoki, ragweed, white hippo, yomogi, kamogaya, timothy, and hargaya. In addition, allergens derived from dog hair and dandruff (Can f1, Can f2), allergens derived from cat hair and dandruff (Fel d1), allergens derived from cockroaches (Brag1, Bra g2), and allergens derived from mold (Brag1, Brag2). Alt a1), allergens derived from natural rubber latex and the like can be mentioned. Among these, mite-derived allergens and cedar pollen-derived allergens are regarded as particularly important as allergens that need to be reduced. By using the composition of the present invention and the non-woven fabric, fiber or textile product obtained by processing the composition of the present invention, various allergens listed above can be reduced and various allergens can be substantially eliminated. can.

As an application of the allergen-reducing composition of the present invention, for example, processing into a nonwoven fabric, fiber or textile product can be considered, and as a method of use thereof, a method such as dipping, coating or spraying in the nonwoven fabric, fiber or textile product can be considered. Can be processed by. Textiles or textile products include clothing, carpets, sofas, wallpaper, interiors such as curtains, duvet side areas, duvet covers, duvet batting, sheets, pillowcases, mats and other bedding, car seats, car mats and other automobiles. Examples include parts and stuffed fabrics, and examples of the non-woven fabric include a wet wiper for cleaning, a mask, a filter material, and a dust collecting bag for an electric vacuum cleaner.

There are various non-woven fabrics and fibers that can process the allergen-reducing composition of the present invention, and examples thereof include nylon, cotton, polyester, wool, etc., and composite fibers using two or more of these fibers. It doesn't matter. It can also be used for non-woven fabrics made of polyethylene or polypropylene. The method for processing the allergen-reducing composition of the present invention into a nonwoven fabric, fiber or textile product is not particularly limited, but dipping treatment, spray treatment, exhaustion treatment and the like can be performed.

Examples of building interior materials include wallpaper using resin such as vinyl chloride, ceiling materials, wood materials such as plywood, floor materials, etc., and surface treatment agents and coating agents for surface-treating these interior materials. , Paints, etc. are also included. When the allergen-reducing composition of the present invention is treated on these building interior materials, it is preferable to perform the treatment by surface treatment. In particular, it can be effectively processed by adding it to a water-soluble or water-based surface treatment agent or coating agent. Further, for the paint, it is preferable to add it to the water-based paint.

As the water-based surface treatment agent, those commercially available as industrial products can be generally used. Such a surface treatment agent is not particularly limited, and examples thereof include various modified starches such as starch and enzyme-modified starch, water-soluble polymers such as polyvinyl alcohol, polyacrylamide, and carboxymethyl cellulose, and acrylic resin emulsions. , Vinyl acetate resin emulsion, acrylic-styrene resin emulsion, acrylic-vinyl acetate resin emulsion, vinyl chloride resin emulsion, vinyl chloride-acrylic resin emulsion, urethane resin emulsion and other aqueous resin emulsions. For the allergen-reducing wallpaper of the present invention, it is preferable to use a water-based resin emulsion that can be expected to have water resistance of the cured film, rather than using a water-soluble polymer. "Aqueous" means that the polymer contained in the surface treatment agent is soluble in water, or that the water-insoluble polymer is dispersed in water or a polar solvent in the form of a resin emulsion. Such an aqueous surface treatment agent can be mixed with water in any ratio macroscopically and uniformly.

For example, Boncoat (registered trademark, manufactured by DIC Co., Ltd.) is used as an acrylic resin emulsion, and Viniblanc (registered trademark, Nisshin Kagaku) is used as a vinyl chloride resin emulsion or a copolymer resin emulsion of vinyl chloride and acrylic acid ester or vinyl acetate. Examples of urethane-based emulsions include Superflex (registered trademark, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adeka Bontita (registered trademark) HUX (manufactured by ADEKA Corporation), and the like.

When the allergen-reducing composition of the present invention is processed for the various uses listed above, the allergen-reducing composition can be made into a suitable formulation for processing so that the processing can be easily performed. Examples of such a preparation include a water-soluble agent dissolved in water or a water-soluble solvent, an oil or emulsion having a high solubility in a water-insoluble agent, and powders and granules held on an appropriate carrier. Of these, a water-soluble agent dissolved in water or a water-soluble solvent is preferable.

When the allergen-reducing composition of the present invention is applied as a spray agent, it is suitable to use a water-based liquid preparation, and the total of the zinc-containing compound and the zirconium salt as the active ingredient is 0.01 to. It is contained in the range of 20%, preferably 0.1% to 5.0%, and more preferably 0.1 to 2%. It is also possible to add a volatile organic solvent in order to improve the drying property when sprayed. There are no particular restrictions on such an organic solvent, but ethanol is an example of a highly volatile solvent that does not pose a safety problem. Further, it is also possible to add a fragrance, a deodorant component, an antibacterial component and the like as other components to the spray agent.

The above spraying agent can be applied to living spaces such as indoors and spaces in vehicles such as cars and trains, and reduces various allergens such as mites and pollen that are present in the space due to adhesion or floating. It becomes possible to do.

It is possible to add a surfactant for the purpose of improving stability and the like in the preparation. The surfactant is not particularly limited, and examples thereof include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. The type of nonionic surfactant is not particularly limited, but for example, polyoxyethylene alkyl phenyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, sorbitan fatty acid ester, poly. Examples thereof include oxyethylene sorbitan fatty acid ester. Examples of the anionic surfactant include alkylbenzene sulfonate, polyoxyethylene alkyl phenyl ether sulfate, dialkyl sulfosuccinate and the like. Examples of the cationic surfactant include aliphatic amine salts and quaternary ammonium salts thereof, and examples of the amphoteric surfactant include betaine-type surfactants and aminocarboxylates. Further, these nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants may be used alone or in combination of two or more.

It is also possible to further add a known allergen-reducing component to the allergen-reducing composition of the present invention as long as the physical properties are not impaired. Examples of the allergen-reducing component include hydroxybenzoic acid-based compounds such as dihydroxybenzoic acid and 2,4,6-trihydroxybenzoic acid or salts thereof, polystyrene-based compounds such as parahydroxypolystyrene and polystyrene sulfonate, and natural products such as persimmon astringent. Examples thereof include extracts and inorganic salt compounds such as calcium salts and strontium salts.

When the allergen-reducing composition of the present invention is used for the purpose of removing allergens from indoor dust mites, the allergen-reducing effect can be further sustained by processing at the same time as the acaricide. The acaricide used is not particularly limited as long as it has a lethal effect or a repellent effect on indoor dust mites, and is, for example, benzyl alcohol, benzyl benzoate, phenyl salicylate, cinnamaldehyde, hisop oil, carrot seed oil. Etc., and pyrethroid compounds such as natural pyrethrin, phenothrin, permethrin, organophosphorus compounds such as fenitrothion, malathion, fenthion, diazinon, dichophor, chlorbenzylate, hexithiazox, tebufenpyrado, pyridaben, amide flumeth and the like are used. be able to.

The allergen-reducing composition of the present invention may be concerned about the growth of mold or fungi. Therefore, it is possible to use an antifungal agent or an antibacterial agent in combination at the same time. The type of the antifungal agent or the antibacterial agent is not particularly limited as long as it has an antifungal or antibacterial effect, and for example, 5-chloro-N-methylisothiazolone, methylenebisthiocyanate, 2-bromo-2-nitropropane- 1,3-diol, glutaaldehyde, iodopropynylbutylcarbamate, zinc salt of pyridinethiol-N-oxide, 1,2-benzoisothiazolone, 1,2-dibromo-2,4-dicyanobutane, chlorhexidine gluconate, 2- Isopropyl-5-methylphenol, 3-methyl-4-isopropylphenol, orthophenylphenol, methyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, butyl paraoxybenzoate, parachloromethoxylenol, parachloromethacresol, Polylysine, benzalkonium chloride, didecyldimethylammonium chloride, Nn-butylbenzoisothiazolone, N-octylisothiazolone, 2- (4-thiazolyl) benzimidazole, methyl 2-benzimidazolylcarbamate, tetrachloroisophthalonitrile, Diiodomethylparatril sulfone, parachlorophenyl-3-iodopropagilformal, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, fatty acid glycerin ester, hinokithiol and the like can be used.

In formulating the allergen-reducing composition of the present invention, in addition to the above-mentioned surfactant, antistatic agent and antibacterial agent, if necessary, a chelating agent, a rust preventive agent, a fragrance, an antistatic agent and an antifoaming agent. , Antistatic agents, resin binders, thickeners, softening agents and the like can also be added.

Examples of the usage form of the allergen-reducing composition of the present invention include spraying agents and processing agents, and compositions that may come into contact with humans in the environment, such as softeners, deodorants, and fungicides, It is also possible to reduce allergens in the environment by adding them to disinfectants, pesticides, paints, adhesives, etc., and materials that humans may come into contact with in the environment, such as wood, concrete and metal. It is also possible to reduce allergens in the environment by processing building materials such as stone and glass into molded products made of rubber, paper, resin and plastic.

The present invention will be described in more detail with reference to Examples and Test Examples, but the present invention is not limited thereto. In addition, all% shown below are weight%.

The following reagents and the like were used as raw materials for the preparation of Examples and Comparative Examples.

Zinc gluconate (Helcious Zn (registered trademark), manufactured by Fuso Chemical Industry Co., Ltd.)
Basic zinc carbonate (manufactured by Sakai Chemical Industry Co., Ltd.)
Basic potassium zirconium carbonate (approx. 50%) (Zirmel 1000 (registered trademark), manufactured by Nippon Light Metal Co., Ltd.)
Basic zirconium chloride (about 45%) (Zircozol ZC-2 (registered trademark), manufactured by Daiichi Rare Element Chemical Industry Co., Ltd.)
Zinc oxide (manufactured by Wako Pure Chemical Industries, Ltd.)
Zinc chloride (manufactured by Wako Pure Chemical Industries, Ltd.)

[Basic zinc carbonate dispersion]
20 g of basic zinc carbonate, 1 g of Poise (registered trademark) 520 (manufactured by Kao Co., Ltd.), and 79 g of ion-exchanged water are mixed, and wet pulverization is performed using glass beads having a diameter of 1 mm for 10 minutes to obtain 20% basic zinc carbonate. A dispersion was obtained and used as a basic zinc carbonate dispersion.

[Zinc oxide dispersion]
20 g of zinc oxide, 1 g of Poise 520 (manufactured by Kao Corporation), and 79 g of ion-exchanged water are mixed and wet-ground with glass beads having a diameter of 1 mm for 10 minutes to obtain a 20% zinc oxide dispersion to obtain zinc oxide. It was used as a dispersion.

[Zinc hydroxide dispersion]
Dissolve 23.3 g of zinc chloride in 100 g of ion-exchanged water, add a 10% aqueous solution of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) to this solution, adjust the pH to 9.5, and add zinc hydroxide. Precipitated. Further, 0.5 g of Kelzan S Plus (manufactured by Sansho Co., Ltd.) was added, and ion-exchanged water was further added to make 168 g, and then the mixture was further stirred for 1 hour to obtain a 10% zinc hydroxide dispersion to obtain zinc hydroxide dispersion. It was made into a liquid.

Examples 1 to 18 were prepared with the formulations shown in Tables 1 to 3, and Comparative Examples 1 to 12 were prepared with the formulations shown in Tables 4 to 5.

[Test Example 1]
Measurement of Dania Allergen Reduction Effect by Allergen Reduction Composition Examples 1 to 18 with respect to an allergen solution containing the dania allergen Der f2 and having a protein amount of 900 ng / 1 mL {phosphate buffer (pH 7.2)}. , Comparative Examples 1 to 12 were each reacted with 50 μL of a solution diluted 10-fold with ion-exchanged water. For these samples, the mite allergen reduction effect was measured by the sandwich method of Der f2 enzyme-linked immunosorbent assay (ELISA). First, 100 μL of the anti-Der f2 monoclonal antibody 15E11 diluted with a phosphate buffer (pH 7.4) to 2 μg / mL was added to each well of the F16 MAXISORP NUNC-IMMUNO MODEULE plate (manufactured by NUNC) at 4 ° C. I was sensitized for 3 days. After sensitization, the solution was discarded, 200 μL of blocking reagent {1 wt% bovine serum albumin + phosphate buffer (pH 7.2)} was added per well, and the mixture was reacted at 37 ° C. for 60 minutes. After the reaction, the plate was washed with phosphate buffer (pH 7.2).

Next, 100 μL of the extract obtained by reacting the mite allergen with the above composition was added dropwise per well, and the mixture was reacted at 37 ° C. for 60 minutes. After the reaction, the plate was washed with phosphate buffer (pH 7.2). Peroxidase-labeled anti-Der f2 monoclonal antibody was dissolved in phosphate buffer {pH 7.2, containing 1 wt% bovine serum albumin and 0.05 wt% polyoxyethylene (20) sorbitan monolaurate} at 200 μg / mL. A solution diluted 1200-fold with phosphate buffer (pH 7.2, containing 1 wt% bovine serum albumin and 0.05 wt% polyoxyethylene (20) sorbitan monolaurate) was added in an amount of 100 μL per well. .. After reacting at 37 ° C. for 60 minutes, the plate was washed with phosphate buffer (pH 7.2). To 6.5 mL of 0.1 mol / L phosphate buffer (pH 6.2), add 1 tablet of ortho-phenylenediamine dihydrochloride (13 mg Tablet, manufactured by Wako Pure Chemical Industries, Ltd.) and 6.5 μL of 30% hydrogen peroxide solution. 100 μL of hydrogen peroxide was added per well, and the mixture was reacted at 37 ° C. for 3 minutes. Immediately after that, 50 μL of 1 mol / L H ₂ SO ₄ was added to stop the reaction, and the absorbance (OD490 nm) was measured with a spectrophotometer for microplates (manufactured by Tecan Japan Co., Ltd.). The Der f2 concentration was obtained from the absorbance, and the reduction rate was calculated by the formula (1). The results are shown in Tables 6-7.

Decrease rate (%) = (900- (Der f2 amount)) / 900 × 100 (1)

[Test Example 2]
Measurement of allergen reduction effect of Japanese cedar pollen allergen by the allergen reduction composition Examples 1 to 18 were compared with the allergen solution of 12.5 ng / 1 mL {phosphate buffer (pH 7.2)} as the Japanese cedar pollen allergen Cry j1. 25 μL of each of Examples 1 to 12 diluted 10-fold with ion-exchanged water was reacted. For these samples, the effect of reducing cedar pollen allergen was measured by the sandwich method of Cry j1 enzyme-linked immunosorbent assay (ELISA). First, Cry j1 monoclonal antibody 013 diluted to 2 μg / mL with phosphate buffer (pH 7.4, _{containing 0.1 wt% NaN 3} ) was added per well of the F16 MAXISORP NUNC-IMMUNO MODULE plate (manufactured by NUNC). 100 μL was added and sensitized at 4 ° C. for 1 day. After sensitization, discard the solution and add blocking reagent {1 wt% bovine serum albumin + phosphate buffer (pH 7.2, _{containing 0.1 wt% NaN 3} )} in an amount of 200 μL per well at 37 ° C., 60. Reacted for minutes. After the reaction, the plate was washed with phosphate buffer {pH 7.2, containing 0.1 wt% polyoxyethylene (20) sorbitan monolaurate}.

Next, 100 μL of a cedar pollen allergen extract sample contacted with the processed non-woven fabric was added dropwise per well, and the mixture was reacted at 37 ° C. for 60 minutes. After the reaction, the plate was washed with phosphate buffer {pH 7.2, containing 0.1 wt% polyoxyethylene (20) sorbitan monolaurate}. Peroxidase-labeled Cry j1 monoclonal antibody 053 was dissolved in distilled water at 200 μg / mL and dissolved in phosphate buffer {pH 7.2, 1 wt% bovine serum albumin and 0.1 wt% polyoxyethylene (20) sorbitanmono. A solution diluted 1200-fold with laurate-containing} was added in an amount of 100 μL per well. After reacting at 37 ° C. for 60 minutes, the plate was washed with phosphate buffer {pH 7.2, containing 0.1 wt% polyoxyethylene (20) sorbitan monolaurate}. Add 100 μL of ortho-phenylenediamine dihydrochloride (manufactured by SIGMA CHEMICAL CO.: 26 mg Tablet) and 13 μL of hydrogen peroxide solution to 13 mL of 0.1 mol / L phosphate buffer (pH 6.2). , 37 ° C. for 5 minutes. Immediately after that, _{50 μL of 2} mol / L H 2 SO ₄ was added to stop the reaction, and the absorbance (OD490 nm) was measured with a spectrophotometer for microplates (manufactured by Tecan Japan Co., Ltd.). The Cry j1 concentration was obtained from the absorbance, and the reduction rate was calculated by the formula (2). The results are shown in Tables 8-9.

Decrease rate (%) = (12.5- (Cry j1 amount)) /12.5 × 100 (2)

[Test Example 3]
Processing of PVC wallpaper into a surface treatment agent

Preparation of PVC wallpaper As the surface layer of PVC wallpaper, 100 g of PVC powder (PQB83, manufactured by Shin-Daiichi PVC Co., Ltd.) with an average degree of polymerization of 700, 50 g of plasticizer diisononyl phthalate (DINP, manufactured by Taoka Chemical Industry Co., Ltd.), and Adecastab as a stabilizer. FL100 (manufactured by ADEKA Co., Ltd.) 3 g and isoparaffin (IP solven 2028, manufactured by Idemitsu Kosan Co., Ltd.) 7 g were mixed using a stirrer. The prepared surface layer liquid was applied to A4 size PPC paper as a base layer so as to be about 200 g / m2, and heated at 150 ° C. for 1 minute to obtain a vinyl chloride wallpaper.

Urethane-based resin emulsion (Viniblanc HD-065 (registered trademark), manufactured by Nisshin Kagaku Kogyo Co., Ltd.) was used as a surface treatment agent, and 20% of Example 16, Comparative Example 4, and Comparative Example 6 were added thereto to make it uniform. Was mixed with. This surface treatment agent was applied to the vinyl chloride sheet at a rate of 10 g / m2 and dried at room temperature to obtain an allergen-reduced wallpaper.

A sample of these allergen-reduced wallpaper was cut into a circle with a diameter of 8 cm, and the edge portion of the wallpaper sample was bent by about 5 mm so that the surface coated with the surface treatment agent became concave. Spread 1 mL of an aqueous mite allergen solution (Der f2 concentration 900 ng / mL) on this, and align the processed surface with the same sample in which the edge portion of about 5 mm is bent so that the surface on which the allergen-reducing composition is processed is convex. I sandwiched it like this. This was placed in a plastic bag with a chuck to prevent the allergen aqueous solution from volatilizing, stored at room temperature for 1 hour, and 100 μL of the allergen aqueous solution was recovered using Pipetman, and the same method as in [Test Example 1] was used. The amount of dania allergen was measured. The results are shown in Table 10.

[Test Example 4]
Measurement of allergen reduction effect on processed non-woven fabric 50 g of a solution obtained by diluting Examples 16 and Comparative Examples 4 and 6 with ion-exchanged water about 100 times, and 80 g / m ² polypropylene non-woven fabric (20 cm × 15 cm) for 1 minute. It was soaked, treated with a squeezing rate of about 200%, and then dried at 100 ° C. for 15 minutes. Cut a sample of these allergen-reduced non-woven fabrics into 5 cm x 5 cm, put them in a plastic bag with a chuck, and further put them in a dania allergen aqueous solution (Der f2 concentration 900 ng / mL) or a cedar pollen allergen aqueous solution (Cry j1 concentration 12.5 ng / mL). 1 mL was added. Store at room temperature for 1 hour, collect 100 μL of allergen aqueous solution using Pipetman, and measure the amount of dania allergen or cedar pollen allergen using the same method as in [Test Example 1] or [Test Example 2]. went. The results are shown in Tables 11 and 12.

By using the allergen-reducing composition of the present invention containing a zinc-containing compound and a water-soluble zirconium salt, allergens such as mites and pollen can be reduced, and non-woven fabrics, filter materials, fibers or Provides allergen-reducing compositions for imparting the function of reducing allergens to textile products, and building interior materials such as non-woven fabrics, filter materials, textiles or textile products, wallpaper, flooring materials, ceiling materials, etc. that can reduce allergens. can do.

Claims (3)

Allergen reduction characterized by containing (A) one or more selected from zinc hydroxyate, zinc carbonate, basic zinc carbonate, zinc oxide or zinc hydroxide , and (B) basic zinc carbonate. Composition. A surface treatment agent containing the allergen-reducing composition according to claim 1 and water or a water-soluble solvent. Nonwoven fabric, wallpaper, filter material, fiber or textile product, building interior material processed with the allergen reduction composition according to claim 1.